US20150025187A1 - Monobenzoate useful as a plasticizer/coalescent in polymeric dispersions - Google Patents

Monobenzoate useful as a plasticizer/coalescent in polymeric dispersions Download PDF

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US20150025187A1
US20150025187A1 US14/378,574 US201314378574A US2015025187A1 US 20150025187 A1 US20150025187 A1 US 20150025187A1 US 201314378574 A US201314378574 A US 201314378574A US 2015025187 A1 US2015025187 A1 US 2015025187A1
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coalescent
plasticizers
coalescents
plasticizer
opv
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William D. Arendt
Emily MCBRIDE
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Emerald Kalama Chemical LLC
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Assigned to EMERALD KALAMA CHEMICAL, LLC reassignment EMERALD KALAMA CHEMICAL, LLC RELEASE OF SECURITY INTEREST IN PATENTS - SECOND LIEN Assignors: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
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    • C09D11/00—Inks
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
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    • C08K5/00—Use of organic ingredients
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    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
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    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined

Definitions

  • This invention is directed to a non-phthalate monobenzoate useful as a plasticizer or coalescent in a variety of polymer applications, including but not limited to architectural coatings, industrial coatings, OEM coatings, paints, enamels, lacquers, inks, overprint varnishes (“OPV's”), other coatings, polishes and the like,
  • this invention is directed to the use of a monobenzoate ester, 3-phenyl propyl benzoate, in coatings applications, to provide compatibility, lower VOC content, and excellent film forming properties.
  • the invention provides compositions that have comparable or better rheology, viscosity stability, compatibility, processability, gloss, hardness, scrub and rub resistance, water and alkali resistance, adhesion, color density, and film formation, among other advantages, over traditional plasticizers or coalescents.
  • the invention is also directed to polymeric compositions comprising the inventive monobenzoate, such as architectural and industrial coatings, paints, OEM coatings, special purpose coatings, OPV's, inks, nail polish, floor polish and other polymeric coatings.
  • inventive monobenzoate such as architectural and industrial coatings, paints, OEM coatings, special purpose coatings, OPV's, inks, nail polish, floor polish and other polymeric coatings.
  • the film-forming aid i.e., coalescent
  • the film-forming aid i.e., coalescent
  • the film-forming aid is a very important component.
  • Coalescents allow film formation to occur at lower temperatures than the polymer without the coalescent would. Typically, about is the temperature to which a coalescent must reduce the minimum film formation temperature (MFFT) of a polymer.
  • MFFT minimum film formation temperature
  • the coalescent provides formation of a film with improved properties as compared to a film without the coalescent.
  • Tg glass transition temperatures
  • coalescents allow film formation to occur at desired ambient conditions, whereas a continuous film would not form with such polymers without the coalescent.
  • Coalescents partition to the polymer in the emulsion and soften dispersed particles allowing them to fuse or form a continuous film. The coalescent will then partially or completely volatilize out of the film, depending on the coalescent, allowing the film to regain its original physical properties. Plasticizers, used as coalescents are less volatile and slower to come out of the film.
  • coalescents are selected that improve the properties of the paint/coating film, such as gloss, scrub resistance, and block resistance. Coalescents are also selected based upon a variety of properties, including without limitation, volatility, miscibility, stability, compatibility, ease of use, and cost.
  • Plasticizers have been known and used for years in latex paints and other coatings, primarily for their excellent coalescent properties, In some instances, they are also desired for their plasticizer function at higher levels of use.
  • a typical plasticizer softens a polymer and makes it more workable. It is also well-known that plasticizers can improve paint performance characteristics, such as mud cracking, wet edge and open time.
  • VOC content of the plasticizer/coalescent in the resulting film is the VOC content of the plasticizer/coalescent in the resulting film.
  • “escaping” or “volatilizing” coalescent contributes significantly to the VOC's of the film, beginning with the coalescing phase and lasting for a sustained period afterwards. This, in turn can affect the air quality around the film and be manifested as an unpleasant odor.
  • Traditional coalescents are highly volatile and can contribute significantly to the VOC content of a paint or coating and have significant environment and health disadvantages, VOC's readily vaporize or evaporate into the air, where they may react with other elements or compounds to produce ozone. Ozone, in turn, causes air pollution and a host of health concerns including breathing problems, headache, burning, watery eyes and nausea, just to name a few.
  • VOC's are of particular concern in the paint and coatings industry in the manufacture and application of products containing VOC's. Use of VOC's in the manufacture of paint and coatings result in poor plant air quality and worker exposure to harmful chemicals. Persons who are exposed to VDUs may suffer from a number of health problems, including but not limited to several types of cancers, impaired brain function, renal dysfunction and other health problems.
  • VOC-containing paints and coatings who are regularly exposed to harmful VOC vapors may suffer from health problems.
  • VOC-containing products release harmful VOC's into the air as they dry, and become especially concentrated in indoor applications.
  • Indoor VOC levels are routinely 10 times higher than outdoor levels and may be up to 1,000 times higher immediately after painting. Further, although VOC levels are highest during and soon after painting, they continue seeping out for several years. In fact, only 50 percent of the VOC's may be released in the first year. Accordingly, paints and coatings having high VOC content are considered health and environmental hazards, and regulations have been implemented to protect manufacturing workers and end-users.
  • OOV's Waterborne overprint varnishes
  • inks are specific types of coatings that have significant roles in the graphic arts industry. OPV's provide the finishing touch to printed media, protecting ink and printed matter for a wide variety of applications, including but not limited to books, magazines, packaging materials, and other printed matter. These clear coatings also provide visual effects in addition to protecting the underlying ink from damage.
  • OPV's and inks exist having a wide range of compositions. OPV's and inks are selected for use based upon the printing process to be utilized and volume of use OPV's most commonly comprise three forms: waterborne, UV-curable polymeric dispersions, or other solution (solvent) polymers. Waterborne OPV's are all based on polymeric dispersions having a variety of compositions and glass transition temperatures (Tg). A classic type of polymer used in polymeric dispersions, such as OPV's, is a hard styrene acrylic, which has excellent gloss and durability characteristics.
  • OPV's are often exposed to harsh conditions during processing and in use, yet must look perfect when finally placed on display.
  • OPV's may contain various other additives to impart rub resistance and scratch and abrasion resistance.
  • Still other additives may be selected to facilitate the formation of an effective barrier to moisture, oils or other soils and to improve heat resistance. The choice of additive may depend on the final use intended for the graphic art media prepared using an OPV and the volume of that anticipated use.
  • inks are utilized in the graphic arts industry to fit the various printing processes. Like OPV's, waterborne inks often comprise polymeric dispersions. Inks are often “coated” or protected with OPV.
  • New generation polymer emulsions used in OPV's and inks seem to be following the same trends that are found in other coatings. These systems are softer and may not necessarily require any coalescent or plasticizer to form a film under their conditions of use. Heat and/or air flow may be employed to assist in coalescence in graphic arts. However, these approaches to coalescence may result in poor performance properties and their use is thus limited.
  • coalescents for paint include the traditional industry standard film-forming aid, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TXMB).
  • Other coalescents of choice in different coating industry segments include glycol ethers. All of these are invariably 100% volatile by the EPA 24 D2369 volatility test, a method of VOC determination used for paint and other coating systems.
  • the monobenzoate, 2-ethyl hexyl benzoate has been used as a coalescent in OPV's and waterborne inks and is functional, but it still has a fairly high VOC content.
  • formulators reduce the amount of the most volatile components used in the coatings or replace them with lower VOC content components, both of which reduce VOC concerns to some extent, but may result in compromised performance.
  • Other approaches are to use soft polymers with no coalescent (with the sacrifice of performance in some instances), reduction or elimination of glycols used for antifreeze and tooling, or the use of a low VOC plasticizer or coalescent.
  • Plasticizers are useful coalescents for waterborne systems as they have low VOC contribution; however, they impart greater permanence, i.e., they are slower to leave film, and thus less volatile. In some instances, the permanence of plasticizers can be a detriment. In using plasticizers as coalescents, a balance must be struck between greater permanence—and thus lower VOC's—and good final film properties. Desirably, a low VOC content paint or coating should have at a minimum, equivalent performance to paints or coatings having higher VOC content. Toward that end, raw material suppliers continue to develop new, lower VOC products for use in paints and coatings, which do not compromise performance.
  • Plasticizers traditionally used in the coatings industry include di-n-butyl phthalate (DBP), diisobutyl phthalate (DIBP) or butyl benzyl phthalate (BBP). These plasticizers were used when a true plasticizer was required, as is the case when polymers with high Tg's are employed in one application or another. DBP and DIBP have a lower VOC content than traditional coalescents, but are still somewhat volatile, while BBP has a very low VOC content. Apart from VOC content, however, phthalate ester use has some disadvantages, as DBP and BBP uses, in particular, are restricted due to regulatory concerns.
  • Dibenzoate plasticizers have well known utility in coatings. Dibenzoates by their nature are non-phthalates and do not have the restrictions or health concerns associated with phthalates. Benzoates are historical alternatives for the graphic arts industry. Classic dibenzoates used as coalescents include DPGDB as well as blends of DEGDB and DPGDB. Commercial examples of benzoates include K-Flex® DP (DPGDB), K-Flex® 500 (DEGDB/DPGDB blend), K-Flex® 850S (a newer grade of DEGDB/DPGDB blend), and K-Flex® 975 P (a new triblend comprising DEGDB/DPGDB/1,2-PGDB), among many others.
  • DPGDB K-Flex® DP
  • K-Flex® 500 DEGDB/DPGDB blend
  • K-Flex® 850S a newer grade of DEGDB/DPGDB blend
  • K-Flex® 975 P a new triblend comprising DE
  • Monobenzoate esters known to be useful as plasticizers include: isodecyl benzoate (IDB), isononyl benzoate (INB), and 2-ethylhexyl benzoate (BIB).
  • IDB isodecyl benzoate
  • IB isononyl benzoate
  • BIOB 2-ethylhexyl benzoate
  • isodecyl benzoate has been described as a useful coalescent agent for paint compositions in U.S. Pat. No. 5,236,987 to Arendt.
  • 2-ethylhexyl benzoate in a blend with DEGDB and diethylene glycol monobenzoate is described in U.S. Pat. No. 6,989,830 to Arendt et al.
  • isononyl esters of benzoic acid as film-forming agents in compositions such as emulsion paints, mortars, plasters, adhesives, and varnishes is described in U.S. Pat. No. 7,638,568 to Grass at al.
  • Half ester monobenzoates include dipropylene glycol monobenzoate and diethylene glycol monobenzoate, which are byproducts of the production of dibenzoates, but which, most of the time, are not objects of production.
  • Half esters are not known for being high solvators and are less compatible than the corresponding dibenzoate in PVC. However, the half esters are compatible with emulsion polymers, such as acrylic and/or vinyl ester polymers, which are commonly used in paint and coatings applications.
  • Non-phthalate, low VOC plasticizers and coalescents for use in coatings applications. Such alternatives should be compatible with a wide variety of polymers and have lower VOC content and comparable or better performance properties when used in coating applications traditionally requiring plasticizers and/or coalescents. Non-phthalate, low VOC alternatives are particularly desirable in view of the environmental, health and safety issues associated with many traditional plasticizers and coalescents.
  • the monobenzoate, 3-PPB has not been utilized in polymeric applications of the type discussed herein in the past. It has been used and continues to be used in flavoring and fragrance applications. It has also been used as a solubilizer for certain active or functional organic compounds in personal care products as described in U.S. Patent Publication 2005/0152858.
  • inventive plasticizer in paints and other coatings
  • inventive monobenzoate include plastisols, adhesives, sealants and caulks, which are the subject of co-pending applications.
  • Yet another object of the invention is to provide a monobenzoate useful as a coalescent in polymeric dispersions, which has a lower VOC content and achieves comparable or better performance than traditional coalescents, including but not limited to efficiency and compatibility when used in traditional latex emulsions or other polymeric coatings.
  • Still a further object of the invention is to provide a monobenzoate plasticizer, useful as a plasticizer alone or in a blend of plasticizers, for use in paint or other polymeric coatings, which has a lower VOC content and comparable or better performance than traditional coalescents.
  • This invention is directed to a non-phthalate benzoate plasticizer useful as coalescent for polymeric dispersions, such as architectural coatings (paint), industrial coatings, OPV's, inks, and polishes, among others.
  • the invention is directed to the use of a new monobenzoate, 3-phenyl propyl benzoate (3-PPB), component not previously known or used as a plasticizer or coalescent for coating applications.
  • inventive monobenzoate in the same or similar amounts as traditional plasticizers/coalescents results in a lower VOC content and comparable or better performance and handling properties than that achieved with traditional plasticizers or coalescents.
  • inventive monobenzoate has low toxicity and does not have the environmental, health and safety issues associated with traditional phthalate plasticizers or coalescents.
  • the invention is a non-phthalate coalescent, 3-PPB, useful in coatings applications to aid film formation and improve properties such as viscosity, gloss, block resistance, scrub and rub resistance, chemical resistance, dry time, open-time/wet edge, mudcrack resistance, and heat age stability.
  • the invention is an architectural coating, paint, industrial coating, OEM coating, special purpose coating, lacquer, enamel, OPV, ink, nail polish, or floor polish, comprising 3-PPB.
  • the invention is a variety of aqueous or non-aqueous polymer compositions comprising 3-PPB.
  • the invention is a blend of 3-PPB with other plasticizers and coalescents, including solid plasticizers, for use in paint, OPV's, waterborne inks, colorants, and other coatings.
  • FIG. 1 shows the volatility characteristics determined for the neat plasticizers evaluated, using ASTM D2369, 110° C. for one hour.
  • FIG. 2 shows the volatility characteristics determined for the neat plasticizers evaluated, using a TGA isothermal scan at 110° C. for one hour.
  • FIG. 3 illustrates the viscosity response of the binary blends comprising various plasticizers/coalescents.
  • FIG. 4 shows the amount of water required to reduce the viscosity to 150 mPa ⁇ s, a nominal viscosity for comparison
  • FIG. 5 shows the MFFT of the binary blends at plasticizer/coalescent levels of 4% wet.
  • FIG. 6 shows the MFFT of the binary blends at plasticizer/coalescent levels of 4, 6 and 8% wet.
  • FIG. 7 shows the OPV viscosity response obtained with 4% plasticizer/coalescent at 1 day aging.
  • FIG. 8 shows the time to dry to touch for OPV's comprising various plasticizers/coalescents.
  • FIG. 9 shows the gloss data obtained for the OPV's comprising various plasticizers/coalescents (20° gloss on a 3B Leneta substrate).
  • FIG. 10 shows Konig hardness data obtained for the OPV's comprising various plasticizers/coalescents.
  • FIG. 11 shows block resistance results for the semigloss acrylic at 1-clay (RT and 120° F.) for the plasticizers/coalescents evaluated.
  • FIG. 12 shows block resistance results for the semigloss acrylic at 7-day (RT and 120° F.).
  • FIG. 13 shows the scrub resistance results for the semigloss acrylic for the plasticizers/coalescents evaluated.
  • FIG. 14 shows open-time, wet edge results of the semigloss acrylic for the plasticizers/coalescents evaluated.
  • FIGS. 15 ( a ) and ( b ) show heat age stability of the semigloss acrylic, both Delta Viscosity and Delta E Color Shift, respectively, for the plasticizers/coalescents evaluated.
  • FIG. 16 shows the mudcrack resistance of the semigloss acrylic for the plasticizers/coalescents evaluated.
  • FIG. 17 shows the low temperature, touch-up results of the semigloss acrylic for the plasticizers/coalescents evaluated.
  • FIG. 18 shows the block resistance, 7-day results (RT and 120° F.) for the vinyl acrylic flat paint for the plasticizers/coalescents evaluated.
  • FIG. 19 shows the scrub resistance results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated.
  • FIG. 20 shows the open-time/wet-edge results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated.
  • FIGS. 21( a ) and ( b ) show the heat age stability of the vinyl acrylic flat paint, both Delta Viscosity and Delta E color shift results, respectively, for the plasticizers/coalescents evaluated.
  • FIG. 22 shows the mudcrack resistance results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated.
  • FIG. 23 shows the low temperature touch-up results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated.
  • the present invention is directed to a monobenzoate plasticizer useful as a primary or secondary plasticizer/coalescent for aqueous and non-aqueous based polymer coatings, including but not limited to architectural coatings (paint), industrial coatings, OEM coatings, special purpose coatings, OPV's, inks and polishes.
  • the benzoate plasticizer comprises a unique monobenzoate, 3-phenyl propyl benzoate (3-PPB), a known flavor and fragrance component, not previously known or used as a plasticizer or coalescent in polymeric coatings.
  • the inventive monobenzoate plasticizer can generally be utilized as a primary plasticizer, a secondary plasticizer in blends with other plasticizers, or a coalescent with numerous polymeric dispersions, often as a substitute or alternative for conventional plasticizers/coalescents having a higher VOC content.
  • Any of the known polymers that can be formulated into an architectural coating (paint), industrial coating, OEM coating, special purpose coating, nail polish, OPV, ink, floor polish or other similar polymeric coating can be used in combination with the inventive monobenzoate to prepare a low VOC content composition in accordance with the present invention.
  • Suitable polymers include, but are not limited to: various vinyl polymers, such as polyvinyl chloride and copolymers thereof, vinyl acetate, vinyl acrylates, vinyl chloride co- and ter-polymers, vinylidene chloride, diethyl fumarate, or diethyl maleate various polyurethanes and copolymers thereof: cellulose nitrate; polyvinyl acetate and copolymers thereof; various polyacrylates and copolymers thereof, and various esters of versatic acid.
  • various vinyl polymers such as polyvinyl chloride and copolymers thereof, vinyl acetate, vinyl acrylates, vinyl chloride co- and ter-polymers, vinylidene chloride, diethyl fumarate, or diethyl maleate various polyurethanes and copolymers thereof: cellulose nitrate; polyvinyl acetate and copolymers thereof; various polyacrylates and copolymers thereof, and various esters of versatic acid.
  • Acrylic polymer compositions for various applications may also be used with the inventive monobenzoate and include various polyalkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, or allyl methacrylate; or various aromatic methacrylates, such as benzyl methacrylate or styrene acrylate; or various alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate; or various acrylic acids, such as methacrylic acid and other styrenated acrylics.
  • polyalkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, or allyl methacrylate
  • aromatic methacrylates such as benzyl methacrylate or
  • polymers for which the inventive monobenzoate may be useful as a plasticizer include epoxies, polyamides, and nitrocellulose. Still other polymers will be evident to one skilled in the art.
  • inventive monobenzoate is not limited to any particular polymer. Although the invention is described primarily with respect to paint, OPV and ink applications, the inventions is not limited as such. Other polymer-based coating compositions requiring plasticizers and/or coalescents and/or where plasticizers and/or coalescents are traditionally utilized, are known to one skilled in the art.
  • the novel monobenzoate of the present invention may be used as a low VOC substitute or alternative for various traditional polymeric dispersions.
  • the total amount of the inventive monobenzoate used in any particular polymeric dispersion would range broadly depending on the particular polymer, the characteristics of the polymer and other components, the process, the application or use and the results desired. Exemplary amounts for plasticizers/coalescents are included in the examples and further described generally herein.
  • the amount of coalescent required for a polymeric dispersion is based on the MFFT of the base polymer and may be used in an amount sufficient to form a film at room temperature. The harder the polymer (higher MFFT and Tg), the more plasticizer/coalescent required.
  • plasticizer/coalescents can be used in amounts up to about 20% of the polymer solids in the system, depending on the particular polymer.
  • coalescents may be utilized in amounts up to about 20 wt. %, based upon the total weight of the overprint varnish or ink. Exemplary amounts may range from about 2% to about 8% wet.
  • inventive monobenzoate examples include nail polish, floor polish, OEM coatings, and special purpose coatings.
  • nail polish products in particular, phthalates have been used for at least a decade, and certain dibenzoates have also been utilized for several years, wherein the advantages attributable to coalescents discussed herein are desired.
  • the inventive monobenzoate may be, but is not required to be, blended with various other conventional plasticizers to enhance or augment properties of polymer compositions.
  • Conventional plasticizers have been described herein and include, but are not limited to phthalate esters up to C5, phosphate esters, polyesters, citrates, isobutyrates, sulfonamides, sulfonic acid esters, terephthalate esters up to C4, epoxy plasticizers, benzoate esters, including both di- and mono-benzoates, or mixtures thereof.
  • the inventive monobenzoate may also be blended with solid plasticizers, such as sucrose benzoate, dicyclohexyl phthalate, triphenyl phosphate, glycerol tribenzoate, 1,4-cyclohexane dimethanol (CHDM) dibenzoate, pentaerythritol tetrabenzoate, alkyl glycol esters, or mixtures thereof.
  • solid plasticizers such as sucrose benzoate, dicyclohexyl phthalate, triphenyl phosphate, glycerol tribenzoate, 1,4-cyclohexane dimethanol (CHDM) dibenzoate, pentaerythritol tetrabenzoate, alkyl glycol esters, or mixtures thereof.
  • inventive monobenzoate may be combined with or include various amounts of conventional additives such as oils, diluents, antioxidants, defoamers, surfactants, heat stabilizers, flame retardants, surfactants, waxes, solvents and the like, depending on the particular coatings application.
  • additives such as oils, diluents, antioxidants, defoamers, surfactants, heat stabilizers, flame retardants, surfactants, waxes, solvents and the like, depending on the particular coatings application.
  • Additives amounts can generally vary widely and often range from about 0.1 to about 75 parts by weight for every 100 parts by weight of the coating composition.
  • traditional OPV's in addition to the coalescent, comprise a dispersion of a high Tg (>10° C.) polymer, wax dispersions, various high Tg resins, surfactants, defoamers, and water.
  • Traditional inks in addition to the coalescent, comprise similar components as an OPV, but with added pigments for color.
  • the inventive monobenzoate provides a lower VOC content alternative over many traditional coalescents and, depending on the application, provides comparable or better compatibility, viscosity stability, rheology, film formation, gloss, water and alkali resistance, dry to touch time, open time, scrub and rub resistance, color density, adhesion, peel strength and hardness, among other advantages.
  • the inventive monobenzoate outperforms industry standard coalescents, regardless of VOC content, including traditional and newer dibenzoate blends.
  • the monobenzoate is particularly useful as a coalescent when considering the use of harder polymers as alternatives to softer polymers in a variety of low VOC formulations.
  • plasticizers/coalescents were evaluated in a variety of experiments. First, VOC's of the neat plasticizers/coalescents selected were determined. Then, effectiveness and efficiency of the coalescents with a traditional polymer were determined using simple binary blends.
  • a starting basic OPV formulation was prepared to assess the effect of the new plasticizer in an actual OPV.
  • the coalescent performance in a simple waterborne model ink formulation was evaluated. Inks were then coated with the experimental OPV's and evaluated.
  • the polymer selected for use in the OPV/ink examples was a traditional high Tg, hard styrene acrylic emulsion a standard in the graphic arts industry, although it is expected that the present inventive coalescent would be useful in a large number of polymeric dispersions used in this industry. Such polymers would be known to one skilled in the art.
  • the polymer was utilized in all of the simple starting formulations set forth herein.
  • plasticizers/coalescents were selected for evaluation in the examples (in whole or part):
  • plasticizers/coalescents and TMPDMB are not soluble in water but the DPM, BCL and C are completely or partially soluble in water. It is expected that the water insoluble plasticizers/coalescents will partition to the polymer in the dispersion.
  • Viscosity Response Both the initial and 24 hour viscosities were measured. Viscosity measurements were made using a Brookfield RVT at 20 RPM's for 10 revolutions at 23 ⁇ 2° C.
  • MFFT Minimum Film Formation Temperature
  • Gloss The gloss of the substrate or the print was measured at 20° and 60° with a Micro-TRI-Gloss II Meter. ASTM D523 employed.
  • Alkaline Resistance Two drops of alkaline solution (Clorox® Formula 409) was applied to the print, covered with a watch glass, and timed for 2, 5 or 10 minutes. After the allotted time, the solution was removed gently with a folded KimwipeTM. The punt and KimwipeTM were examined and rated. The rating was 5—no effect; 4—slight blush: 3—blush: 2—partial break; 1—total break in film.
  • Rub Resistance was evaluated using 5 layers of cheesecloth under a 1 kg weight. The cheesecloth and the weight were rubbed against the ink or the OPV covered ink 100 times. The cheesecloth was then evaluated and rated. The rating was—5—no effect; 4—slight blush; 3—blush; 2—partial break; 1—total break in film.
  • the OPV was coated on an aluminum panel using a 3 mil drawdown. Samples were then dried for 4 hours and tested using a Konig Pendulum Tester. Samples were tested 4 hours, 24 hours, 3 days and 7 days after preparation. ASTM D4366 employed.
  • Optical Density and Color of Ink The optical density (color strength) of the prints was measured with an X-Rite Color 17 spectrophotometer. ASTM D2066 employed.
  • Viscosity of Ink The viscosity of the ink prepared was determined with a TA AR2000ex rheometer. Two centimeter plates with a gap of 100 microns were used at 25° C. The shear rate was 100 sec ⁇ 1 .
  • Diblend Formulations Made by adding the coalescent slowly to the emulsion at 500 RPMs using a high speed mixer equipped with a Jiffy blade. Once the coalescent was added, the speed was increased to 750 RPM for a total mix time of 30 minutes.
  • Basic OPV Formulations Prepared by adding the individual components in order to the mixing vessel while mixing at 500 RPM's using a high speed mixer equipped with a jiffy blade. The coalescent was the last to be added. This mixture was stirred for a total of 5 minutes at 500 RPM's after the add of the last component, then the speed of the mixer was increased to 750 RPM's for an additional 5 minutes.
  • the gloss, water resistance, alkaline resistance, rub resistance and adhesion to the prints were evaluated both when the prints were first made, and after aging for 3 days.
  • the OPV was applied with a #6 Mayer wound rod, depositing approximately 15 ⁇ m wet film on a 3B Leneta card, a clay coated board or over a blue flexographic ink on a 3B Leneta card, oxidized polypropylene film or clay coated board.
  • the inks were drawn down with a Flex® Hand-proofer with a 180 pyramid cell anilox roll on 3B Leneta cards, clay coated boards and the treated polypropylene film.
  • the ink was air dried and then dried in an oven three times for 30 seconds at 70° C.
  • the OPV was applied as above over the hand proofs and was air dried, then dried in an oven three times for 30 seconds at 70° C. Each OPV was matched with the corresponding ink in every case.
  • FIGS. 1 and 2 illustrate the volatility characteristics determined for the neat plasticizers/coalescents evaluated.
  • Traditional ether coalescents were definitely volatile.
  • the plasticizers of the evaluation were all low in volatility and, thus, would not contribute significantly to the overall VOC of a formulation at typical levels of use.
  • the coalescents that were 100% volatile will contribute significantly to the total VOC release.
  • the TGA scan data shows that the monobenzoate of the invention, X-613 (3-PPB), was the most volatile, However, X-613 was significantly lower in VOC content than the older traditional high VOC coalescents. All of the plasticizers/coalescents of the evaluation were considerably lower than 20% volatile compared to the ethers, TMPDMB and 2-EHB.
  • Coalescents were incorporated in a base emulsion at the level of use in a basic starting OPV formulation (4%) to observe the effect of just the coalescent on the base polymer.
  • the important tests to evaluate how coalescents affect the polymer are: viscosity response (indicates interaction and swelling of the polymer), minimum film formation temperature (MFFT), and water reduction.
  • the viscosity response of the base emulsion is indicative of the compatibility of the water insoluble coalescents tested.
  • FIG. 3 illustrates the viscosity response of the binary blends comprising various plasticizers/coalescents. With the exception of TMPDMB, all of the water insoluble coalescents had excellent viscosity response. The result for TMPDMB indicated that it lacked complete compatibility with the base styrenated acrylic polymer used in the blend.
  • FIG. 4 shows the amount of water required to reduce the viscosity to 150 mPa ⁇ s, a nominal viscosity for comparison. The amount of water required in each was as would be expected based on the initial viscosity, and infers that water dilution that can be achieved for the plasticizer/coalescent used.
  • FIG. 5 shows the MFFT of the binary blends with 4% wet plasticizer/coalescent added. Note that this low level of plasticizer had a very positive effect on the reduction of MFFT of the base polymer but did not bring it anywhere near room temperature. This is because a simple binary blend was evaluated, which is not yet a complete formulation.
  • Plasticizers/coalescents (at a level of use of 4%) were incorporated in the basic starting formulation listed in Table 1. The viscosity response and dry film properties were determined.
  • the viscosity response of the base emulsion is indicative of the compatibility of the plasticizer/coalescent tested.
  • FIG. 7 illustrates the OPV viscosity response obtained with 4% plasticizer/coalescent at 1 day aging.
  • the viscosities of the dibenzoate OPV's were all in the range expected—the triblend X 20, the inventive monobenzoate X 613 and the diblend X 250 were comparable to DEGDB, 2-EHB, and BC (diethylene glycol monobutyl ether) (in the 100-150 mPa range). Viscosity response for DPM was lower. This coalescent is water soluble and did not partition (at least not completely) to the polymer.
  • Table 2 lists the MFFT's obtained for the OPV formulations. All of the formulations formed films well at room temperature conditions. The water soluble coalescent types were more effective in MFFT suppression. As the MFFT depression Was somewhat less for the dibenzoates than the ethers, the MFFT's of OPV's with loading at 6% wet on the two dibenzoate blends discussed above (X250 and X20) were also determined. These results are also listed in Table 2 and indicate that less than an additional 2% would be necessary to achieve results similar to the ethers. Most likely, 2% additional plasticizer would not be necessary to achieve the desired development of full performance characteristics.
  • FIG. 9 lists the gloss data obtained for the OPV's. There was little difference in the 20° gloss values between the formulations with or without coalescents. This was likely due to the use of the solution resin and its contribution to gloss in the total formulation as well as the coalescent/plasticizer level.
  • Tables 3, 4 and 5 list the water and alkali resistance of the evaluation OPV's.
  • the water resistance initial 1 day OPV on Leneta 3B charts was not nearly as good as the films aged for 3 days.
  • the initial water resistance of the benzoate plasticized films were not as good as could be expected, as plasticizers will normally improve the water resistance of a film. Other factors in the formulation seem to come to bear in the OPV. After three days the water resistance was improved. On the clay coated board the benzoate films have good initial water resistance.
  • FIG. 10 displays the hardness data obtained for the OPV's.
  • Plasticizers often get a bad rap in coatings, where the belief is that as they are more permanent than coalescents they will stay and soften the films too much, resulting in poor performance.
  • the data presented in FIG. 10 is contrary to the “too soft” statement, disproving this generally held misbelief.
  • low VOC plasticizers/coalescents will not necessarily soften too much.
  • the 6% plasticizer films are somewhat softer, but they are somewhat over coalesced. Less is better and acceptable.
  • the 4% OPV's are all similar to the much more volatile coalesced OPV's.
  • a waterborne ink is an OPV with color added. Inks were prepared based on each coalescent/plasticizer using the basic formulation set forth in Table 6 below.
  • the ink was used under an OPV having the same coalescent/plasticizer type. In each case, plasticizer/coalescent was present at 4% in the ink and the OPV.
  • the focus of this example is on the inventive monobenzoate, X-613.
  • the viscosities obtained for the inks were 317 mPa ⁇ s for the “no coalescent” ink, 758 mPa ⁇ s for X-613 ink, 411 mPa ⁇ s for DPM ink and 251 mPa ⁇ s for the C ink. Again, lower viscosities were noted for the inks having water soluble coalescent.
  • Table 7 lists the gloss data obtained on the OPV over ink. Plasticizers/coalescents improve gloss. X-250 was the best of the plasticizers in this respect and similar to the ether coalescent.
  • Table 8 lists the rub data obtained for the inks and the inks coated with OPV on Leneta 3B and on a polypropylene film, The OPV significantly improved the rub resistance of the film. No significant differences in the performance between the evaluation ink and OPV's was noticed.
  • Tables 9, 10 and 11 list the tape adhesion data obtained for the OPV/ink.
  • the coalesced films seem to function better, both initially and after 3 days of dry.
  • the aged films performed well on the clay coated stock.
  • the Dc obtained for the inks did not vary much. They ranged from 1.23 to 1.28 for the evaluation of OPV over ink.
  • coalescent/plasticizers were evaluated:
  • Performance Properties such as block resistance, scrub resistance, dry-time open-time/wet edge, heat age stability, low temperature touch-up, low temperature porosity, mudcrack resistance and freeze-thaw stability.
  • Mudcracking Paint was applied with a Leneta Antisag meter (14-60 mils) on an HK chart at ambient and 40° F. After 24 hour dry the greatest mils without cracking noted. pH ASTM E70 Sag ASTM D4400 Resistance Scrubbability ASTM D2486 - Paint applied at 7 mils wet to a Leneta P121-10N chart and dried at room temperature for 7 days. A 10 shim was employed with abrasive media (SC-2). Failure was a continuous thin line at the shim. Stormer ASTM D562 Viscosity Touch Up Touch up was tested with the paint prepared for the color acceptance. Self-primed Upsom was used and applied with a Linzer 2′′Bristle and polyester brush at RT and 40° F.
  • Table 13 shows the physical property determinations for the semigloss acrylic using the above noted plasticizers/coalescents and a blank.
  • Table 14 shows the rheology results of the semigloss acrylic for the various plasticizers/coalescents evaluated.
  • Table 15 shows the HIDE results of the semigloss acrylic. HIDE results reflect the ability of the coating to cover the substrate completely.
  • FIG. 11 reflects block resistance results of the semigloss acrylic at 1-day (RT and 120° F.) for the evaluated plasticizers/coalescents.
  • 3-PPB performed very well in this test, with no real differences between the samples tested, 3-PPB is a lower VOC content plasticizer/coalescent than TMPDMB, but higher than TEGDO.
  • These block resistance results are important, because they counter the paradigm that a plasticizer, which is thought to have high permanence (lower volatility) than a volatile material, will soften and therefore have poor blocking, as well as other characteristics, such as lower Konig hardness. This data proves that the paradigm is false when it comes to the benzoate family of plasticizers.
  • FIG. 12 shows block resistance results of the semigloss acrylic at 7-day (RT and 120° F.) for the evaluated plasticizers/coalescents. 3-PPB demonstrated excellent performance, much better than TMPDMB and TEGDO.
  • FIG. 13 shows the scrub resistance results of the semigloss acrylic for the plasticizers/coalescents evaluated. Results show that 3-PPB performed very well, at least as good as TMPDMB, the industry standard, and slightly better than TEGDO.
  • Table 16 shows the dry time in minutes of the semigloss acrylic for the evaluated plasticizers/acrylics. While faster is good, that must be balanced against open time. Results show that 3-PPB performed similarly to the other evaluated plasticizers/coalescents.
  • FIG. 14 shows open-time, wet edge for the semigloss acrylic for the plasticizers/coalescents evaluated. The results show that 3-PPB performs at least as good as the other plasticizer/coalescents and in some instances better.
  • FIGS. 15 ( a ) and ( b ) show heat age stability results, both Delta viscosity and Delta E, color shift, respectively, of the semigloss acrylic for the plasticizers/coalescents evaluated. Not a lot of difference was perceived between the various plasticizer/coalescents in terms of viscosity changes or Delta E.
  • FIG. 16 shows the mudcrack resistance results of the semigloss acrylic for the plasticizers/coalescents evaluated. Results were reported for ambient sealed, ambient unsealed, 40° F. sealed and 40° F. unsealed. There were no basic differences between any of the plasticizers/coalescents evaluated.
  • Table 17 below shows the low temperature film formation/porosity results of the semigloss acrylic for the plasticizers/coalescents evaluated. The results show a performance advantage for 3-PPB.
  • FIG. 17 reflects the low temperature, touch-up results of the semigloss acrylic for the plasticizers/coalescents evaluated. Basically, there was no difference between the various plasticizers/coalescents evaluated, although TMPDMB and 3-PPB showed a slight advantage over TEGDO in color.
  • Tables 18, 19 (rheology) and 20 (HIDE), below, show the physical properties of the vinyl acrylic flat paint for plasticizers/coalescents evaluated. The results show no differences among the various plasticizers/coalescents evaluated.
  • FIG. 18 shows the block resistance 7-day results (RT and 120° F.) of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. There were no differences between the plasticizers/coalescents evaluated.
  • FIG. 19 shows the scrub resistance results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. There were no significant differences among the various plasticizers/coalescents.
  • Table 21 below reflects the dry time results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. While 3-PPB had a longer dry time, that may be an advantage for wet edge/open time results.
  • FIG. 20 shows the open-time/wet-edge results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. There may be some wet edge advantages with 3-PPB over time.
  • FIGS. 21 ( a ) and ( b ) show the heat age stability, both Delta viscosity and Delta E, color shift results, respectively, of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. Results show that 3-PPB performed comparable to the other plasticizers/coalescents.
  • FIG. 22 shows the mudcrack resistance results of the vinyl acrylic) flat paint for the plasticizers/coalescents evaluated. Results were obtained ambient-sealed; ambient-unsealed; 40° F.-sealed, and 40° F.-unsealed. Results showed that all the plasticizers/coalescents were equivalent.
  • Table 22 shows the low temperature film formation/porosity results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. Results show that all the plasticizers/coalescents performed better than the blank. 3-PPB performed well, but not quite as good as the other samples, indicating that it was not as efficient in film formation in vinyl acrylic flat paint.
  • FIG. 23 shows the low temperature touch-up results of the vinyl acrylic flat paint for the plasticizers/coalescents evaluated. Results show similar performance across the board.

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
US20150038625A1 (en) * 2012-02-14 2015-02-05 Emerald Kalama Chemical, Llc Monobenzoate useful as a plasticizer in adhesive preparations
US11186703B2 (en) 2016-12-12 2021-11-30 Lg Chem, Ltd. Plasticizer composition and resin composition including same

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2731425B1 (en) 2011-09-19 2018-04-11 Fenwal, Inc. Red blood cell products and the storage of red blood cells in containers free of phthalate plasticizer
US11160728B2 (en) 2014-02-20 2021-11-02 Fresenius Kabi Deutschland Gmbh Medical containers and system components with non-DEHP plasticizers for storing red blood cell products, plasma and platelets
CN106715557B (zh) * 2014-09-26 2019-04-12 艾默罗德卡拉玛化学品公司 在塑溶胶组合物中可用作塑化剂的单苯甲酸酯类似物
US10995198B2 (en) 2014-09-26 2021-05-04 Emerald Kalama Chemical, Llc Monobenzoate analogs useful as plasticizers in plastisol compositions
DE102015200498A1 (de) 2015-01-14 2016-07-14 Wacker Chemie Ag Wässrige Polymerdispersionen für Adhäsive
CN105086236B (zh) * 2015-08-14 2017-07-11 联塑科技发展(贵阳)有限公司 一种硬质聚氯乙烯（u‑pvc）塑料及其管件和制作方法
US11359099B2 (en) * 2015-10-02 2022-06-14 The Chemours Company Fc, Llc Hydrophobic extenders in fluorinated surface effect coatings
CN105733491A (zh) * 2016-04-18 2016-07-06 广东普赛达密封粘胶有限公司 一种低tvoc聚氨酯耐候密封胶及其制备方法
CA3026243C (en) 2016-06-01 2023-11-14 Hack S. Kang Ultra low thermo fusion pvc plastisol coating and textile printing ink
WO2017210436A1 (en) * 2016-06-01 2017-12-07 Kang Hack S Ultra low thermo fusion pvc alternative plastisol coating and textile printing ink
US11535769B1 (en) 2016-12-29 2022-12-27 Henkel Ag & Co. Kgaa Solvent free vinyl plastisol composition
KR102236923B1 (ko) * 2017-12-04 2021-04-07 주식회사 엘지화학 가소제 조성물 및 이를 포함하는 수지 조성물
WO2019236342A1 (en) * 2018-06-07 2019-12-12 Eastman Chemical Company Highly filled plastisols
EP3816233A4 (en) * 2018-06-28 2022-03-30 DIC Corporation AQUEOUS RESIN COMPOSITION, COATING AGENT AND ARTICLES
US10793807B2 (en) * 2018-07-19 2020-10-06 International Flavors & Fragrances Inc Organoleptic compounds
JP7264411B2 (ja) * 2018-10-04 2023-04-25 ファルダノフ アレクサンドラ ポリ塩化ビニルフリーの親油性ポリマーベースの芳香性プラスチゾル
KR102211886B1 (ko) * 2019-04-03 2021-02-03 성원판지 주식회사 자체 접착 밀봉되는 친환경 종이 포장재
JP2022527626A (ja) * 2019-04-05 2022-06-02 エメラルド・カラマ・ケミカル・エルエルシー 水性ポリマー膜の性質を改良するための低ｖｏｃ多機能添加剤

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5102654A (en) * 1990-04-18 1992-04-07 Revlon, Inc. Nail enamel emulsion lacquer comprising a water phase and a lacquer phase
US20020176830A1 (en) * 2001-01-26 2002-11-28 Mui Ronnie F. Phthalate free nail polish enamel composition employing novel plasticizers
US20030185774A1 (en) * 2002-04-02 2003-10-02 Dobbs Suzanne Winegar Cosmetic coating composition comprising carboxyalkyl cellulose ester
US20050152858A1 (en) * 2003-07-11 2005-07-14 Isp Investments Inc. Solubilizing agents for active or functional organic compounds
US20050288205A1 (en) * 2004-01-14 2005-12-29 Finetex, Inc. Phenylethyl benzoate for use in anti-perspirants and personal care products

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1899214A (en) * 1932-02-10 1933-02-28 Eastman Kodak Co Cellulose organic ester composition containing phenylethyl benzoate
GB546716A (en) * 1941-01-25 1942-07-28 John Heron Mcgill Production of improved coatings on fabric supports
GB1155572A (en) * 1965-08-28 1969-06-18 Bridgestone Tire Co Ltd Adhesives for Tyre Cords
GB1103681A (en) * 1966-01-28 1968-02-21 Geigy Uk Ltd Chemical compositions
GB1321383A (en) * 1970-11-12 1973-06-27 Sheller Globe Corp Vinyl chloride resin moulding compositions
US3987001A (en) * 1975-02-03 1976-10-19 Chevron Research Company Ultraviolet protectorant composition
JPS6357550A (ja) * 1986-08-28 1988-03-12 Chisso Corp 安定化エステル系可塑剤の製造方法
US5236987A (en) * 1987-07-02 1993-08-17 Velsicol Chemical Corporation Isodecyl benzoate coalescing agents in latex compositions
US5747573A (en) * 1994-02-07 1998-05-05 H. B. Fuller Licensing & Financing, Inc. High heat resistant hot melt adhesive
US5728760A (en) * 1995-04-11 1998-03-17 Great Lakes Chemical Corporation Use of ring-brominated benzoate compounds as flame retardants and/or plasticizers
JPH0948745A (ja) * 1995-08-04 1997-02-18 Kuraray Co Ltd カルボン酸エステルの製造法
US6300400B1 (en) * 1997-04-18 2001-10-09 Illinois Tool Works Inc. Wallboard adhesive
FR2766834B1 (fr) * 1997-07-29 1999-10-08 Eurocopter France Composition adhesive pour le collage a chaud et procede de collage permettant sa mise en oeuvre
US5990214A (en) * 1997-07-31 1999-11-23 Velsicol Chemical Corporation Liquid glycol benzoate compositions
US5965111A (en) * 1998-05-01 1999-10-12 The Procter & Gamble Company Fast drying water-borne nail polish
US6221571B1 (en) * 1998-12-10 2001-04-24 Eastman Kodak Company Silver halide light-sensitive element
US6130031A (en) * 1998-12-11 2000-10-10 Eastman Kodak Company Photographic element containing a benzolylacetanilide DIR coupler
US6689830B1 (en) * 1999-10-15 2004-02-10 Velsicol Chemical Corporation Film forming compositions containing benzoic acid esters of 8-carbon alcohols as additives
JP2002194159A (ja) * 2000-12-25 2002-07-10 Kanegafuchi Chem Ind Co Ltd 塩化ビニル系ペースト樹脂組成物およびディスポーザブル手袋
BR0207296B1 (pt) * 2001-02-22 2013-05-28 composiÇço para revestimento.
US6939551B2 (en) * 2001-05-21 2005-09-06 Coty Inc. Cosmetic films
US7056966B2 (en) * 2001-08-30 2006-06-06 Velsicol Chemical Corporation Liquid benzoate ester compositions and aqueous polymer compositions containing same as plasticizers
JP2003334441A (ja) * 2002-03-13 2003-11-25 Kyoeisha Chem Co Ltd カルボン酸エステル化用固体酸触媒
US7071252B2 (en) * 2002-09-12 2006-07-04 Velsicol Chemical Corporation Plasticizer compositions for non-aqueous plastisols
DE10249912A1 (de) * 2002-10-26 2004-05-06 Oxeno Olefinchemie Gmbh Benzoesäureisodecyclestergemische, Herstellung und deren Verwendung
US7285587B2 (en) * 2002-12-20 2007-10-23 Eastman Chemical Company Flame retardant polyester compositions for calendering
US7166275B2 (en) * 2003-07-11 2007-01-23 Isp Investments Inc. Compositions containing phenethyl aryl esters as solubilizing agents for active organic compounds
DE10336150A1 (de) * 2003-08-07 2005-03-10 Oxeno Olefinchemie Gmbh Schäumbare Kompositionen, die Benzoesäureisononylester aufweisen
DE10341428A1 (de) * 2003-09-09 2005-03-31 Oxeno Olefinchemie Gmbh Verwendung von Isononylbenzoaten als Filmbildehilfsmittel
CN101107306B (zh) * 2005-01-18 2012-06-20 埃克森美孚化学专利公司 在增塑剂组合物中或涉及增塑剂组合物的改进
US20060241197A1 (en) * 2005-04-25 2006-10-26 Velsicol Chemical Corporation Plasticizer compositions for flexible closed cell foams
US8034860B2 (en) * 2006-07-21 2011-10-11 Eastman Specialties Holdings Corporation Organosol plastisol compositions
WO2008014505A2 (en) * 2006-07-28 2008-01-31 Isp Investments Inc. Blends for improved solubilization of active and functional organic compounds
DE102006038715A1 (de) * 2006-08-18 2008-02-21 Evonik Röhm Gmbh Plastisole auf Basis eines Methylmethacrylat-Mischpolymerisats
US7812080B2 (en) * 2006-12-06 2010-10-12 Genovique Specialties Holdings Corporation Low-color foam compositions
JP2008231370A (ja) * 2007-03-23 2008-10-02 Mitsubishi Rayon Co Ltd 重合体粒子、その製造方法、プラスチゾル組成物および物品
JP5015648B2 (ja) * 2007-04-11 2012-08-29 サイデン化学株式会社 光学用粘着剤組成物および光学機能性フィルム
US20090292058A1 (en) * 2008-05-23 2009-11-26 Velsicol Chemical Corporation Aqueous Polymer Compositions Exhibiting Increased Open Time With Reduced Levels Of Volatile Organic Compounds
US20110028624A1 (en) * 2009-07-30 2011-02-03 Genovique Specialties Holdings Corporation Polymer Compositions That Include High Solvating Plasticizer And Surfactant
US20110118362A1 (en) * 2009-11-13 2011-05-19 Randal Dull Polymers for cardiopulmonary therapies
KR101761288B1 (ko) 2010-12-30 2017-07-25 에메랄드 칼라마 케미칼, 엘엘씨 저 voc 코팅용 신규 디벤조에이트 가소제/응집제 블렌드
EP2814878B1 (en) * 2012-02-14 2018-05-23 Emerald Kalama Chemical, LLC Monobenzoate useful as a plasticizer in plastisol compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5102654A (en) * 1990-04-18 1992-04-07 Revlon, Inc. Nail enamel emulsion lacquer comprising a water phase and a lacquer phase
US20020176830A1 (en) * 2001-01-26 2002-11-28 Mui Ronnie F. Phthalate free nail polish enamel composition employing novel plasticizers
US20030185774A1 (en) * 2002-04-02 2003-10-02 Dobbs Suzanne Winegar Cosmetic coating composition comprising carboxyalkyl cellulose ester
US20050152858A1 (en) * 2003-07-11 2005-07-14 Isp Investments Inc. Solubilizing agents for active or functional organic compounds
US20050288205A1 (en) * 2004-01-14 2005-12-29 Finetex, Inc. Phenylethyl benzoate for use in anti-perspirants and personal care products

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150038625A1 (en) * 2012-02-14 2015-02-05 Emerald Kalama Chemical, Llc Monobenzoate useful as a plasticizer in adhesive preparations
US11186703B2 (en) 2016-12-12 2021-11-30 Lg Chem, Ltd. Plasticizer composition and resin composition including same

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